Selectivity of Reaction Sites for Direct Arylation Polycondensation in Bithiophene Derivatives

Direct arylation polycondensation has recently emerged as the method for the synthesis of π-conjugated polymers. In developing this methodology, site selectivity of the reacting C-H bonds is one of the most important issues. Herein, we investigate the direct arylation polycondensation of bithiophene and dialkylbithiophenes to assess site selectivity. We found that low temperature was a key factor for high selectivity in bithiophene, and that 4,4′-dicyclohexylbithiophene exhibited the highest selectivity among the tested dialkylbithiophenes reaction sites.

[1]  W. Lu,et al.  Direct Arylation Polycondensation: A Promising Method for the Synthesis of Highly Pure, High‐Molecular‐Weight Conjugated Polymers Needed for Improving the Performance of Organic Photovoltaics , 2014 .

[2]  A. McNeil,et al.  Conjugated Polymer Synthesis via Catalyst-Transfer Polycondensation (CTP): Mechanism, Scope, and Applications , 2013 .

[3]  Junxiang Zhang,et al.  C–H Arylation Reaction: Atom Efficient and Greener Syntheses of π-Conjugated Small Molecules and Macromolecules for Organic Electronic Materials , 2013 .

[4]  B. Thompson,et al.  Optimization of direct arylation polymerization conditions for the synthesis of poly(3‐hexylthiophene) , 2013 .

[5]  T. Kanbara,et al.  Direct arylation polycondensation for the synthesis of bithiophene-based alternating copolymers , 2013 .

[6]  Yongfang Li,et al.  Effect of Branched Side Chains on the Physicochemical and Photovoltaic Properties of Poly(3‐hexylthiophene) Isomers , 2012 .

[7]  H. Hayashi,et al.  Synthesis of Thiophene- and Bithiophene-Based Alternating Copolymers via Pd-Catalyzed Direct C-H Arylation. , 2012, ACS macro letters.

[8]  Yongfang Li,et al.  Synthesis and Photovoltaic Properties of Copolymers Based on Bithiophene and Bithiazole , 2011 .

[9]  T. Kanbara,et al.  Polycondensation of Dibromofluorene Analogues with Tetrafluorobenzene via Direct Arylation , 2011 .

[10]  K. Ueda,et al.  A general catalyst for the β-selective C-H bond arylation of thiophenes with iodoarenes. , 2010, Angewandte Chemie.

[11]  Caterina Barillari,et al.  Aminopyrazine Inhibitors Binding to an Unusual Inactive Conformation of the Mitotic Kinase Nek2: SAR and Structural Characterization† , 2010, Journal of medicinal chemistry.

[12]  K. Fagnou,et al.  Palladium-catalyzed benzene arylation: incorporation of catalytic pivalic acid as a proton shuttle and a key element in catalyst design. , 2006, Journal of the American Chemical Society.

[13]  G. Barbarella,et al.  Conformational profile, energy barriers and optical properties of quinquethiophene-S,S-dioxides , 2002 .

[14]  B. Liu,et al.  End-group analysis of blue light-emitting polymers using matrix-assisted laser desorption/ ionization time-of-flight mass spectrometry. , 2002, Analytical chemistry.